Composite Material

ABSTRACT

The invention relates to composite materials, containing (i) a nanoporous polymer foam, which can be obtained by reacting one or more epoxy resins with one or more amphiphilic epoxy resin hardeners in water in a phase inversion polymerization process, and (ii) one or more inorganic fillers and/or inorganic fibers, with the stipulation that hollow glass balls are excluded as fillers. Said composite materials are suitable as heat-insulating materials.

FIELD OF THE INVENTION

The invention relates to specific composite materials and their use ofparticular nanoporous polymer foams as thermal insulation materials.

PRIOR ART

Polymeric epoxy resins have been known for a long time. They aregenerally produced by reacting polyepoxides having an average of atleast two terminal or lateral epoxide groups per molecule withhardeners, in particular amine hardeners which are diamines orpolyamines. These polymeric epoxy resins have a variety of applications,with use as paints and varnishes and coating compositions (applicationof a covering layer to a substrate) dominating.

EP-A-1,518,875 describes specific hardeners for water-based epoxy resinsystems, where these hardeners can be obtained by reacting a mixture of(a) at least one epoxidized polyalkylene oxide selected from the groupconsisting of epoxidized polyethylene oxides, epoxidized polypropyleneoxides and polyethylene-propylene oxides, (b) at least one epoxidizedaromatic hydroxyl compound selected from the group consisting ofbisphenol A epoxides and bisphenol F epoxides and (c) at least onearomatic hydroxyl compound selected from the group consisting ofbisphenol A and bisphenol F to form an intermediate and subsequentlyreacting this intermediate with a polyamine. The use of these hardenersfor producing clear varnishes and coating compositions (application of acovering layer to a substrate, for example for floor coatings) is alsodisclosed.

DESCRIPTION OF THE INVENTION

It was an object of the present invention to provide nanoporous polymerfoams which are suitable as thermal insulation materials. In particular,these materials should have a low thermal conductivity (preferably below0.09 W/m*K) and a high mechanical strength (maximum compressive stresspreferably above 1.0 Mpa).

The present invention firstly provides for a composite materialcomprising (i) a nano-porous polymer foam which can be obtained byreacting one or more epoxy resins with one or more amphiphilic epoxyresin hardeners in water in a phase inversion polymerization (PIP), and(ii) one or more inorganic fillers and/or inorganic fibers, with theproviso that hollow glass beads are excluded as fillers.

As regards the composite material, the components (i) and (ii) can becombined with one another in various ways. Thus, the composite materialcan, for example, comprise the components (i) and (ii) in a layerarrangement. The composite material can also comprise the components (i)and (ii) in such a way that the component (ii) is embedded in a matrixof the component (i); here, preference is given to introducing thecomponent (ii) during the course of the production of the component (i)by phase inversion polymerization.

The invention further provides for the use of the composite materialsaccording to the invention as thermal insulation materials in transportmeans and in industrial and plant construction.

As indicated above, the use according to the invention is aimed at thethermal insulation materials in transport means and in industrial andplant construction. Examples of transport means are automobiles, ships,aircraft, rail vehicles and the like, while examples of industrial andplant construction are containers, vessels, pipes, heating systems,solar plants and the like. The field of thermal insulation systems forthe insulation of buildings is expressly excluded, i.e. is not countedin the use according to the invention.

For the purposes of the present invention, nanoporous polymer foams (i)are polymers which have internal voids. These are sponge-like structureswhich have both macropores and micropores, with the microporesdominating and the micropores having average cross sections in the rangefrom 10 to 500 nm and in particular from 10 to 100 nm.

The nature of the inorganic fillers and/or inorganic fibers (ii) is notsubject per se to any restriction apart from the abovementioned provisothat hollow glass beads are excluded as fillers. As component (ii) ofthe composite materials according to the invention, it is possible touse either exclusively inorganic fillers or exclusively inorganic fibersor a combination of inorganic fillers and inorganic fibers.

In one embodiment, the component (ii) has heat-insulating properties.

The component (ii) is preferably comprised in the composite material inan amount in the range from 2 to 90% by volume, based on the totalvolume of the composite material.

The three-dimensional shape of the inorganic fillers can be chosenfreely; it can be, for example, spherical or ellipsoidal but can alsohave an irregular geometry. Preference is given to using inorganicfillers whose maximum diameter is in the range from 10 nm to 5 mm.

The internal structure of the inorganic fillers can be chosen freely;thus, the fillers can be compact in the sense that they have no internalvoids, but they can also have internal voids. In one variant, theinternal voids of the fillers have maximum diameters in the range from10 to 1000 nm.

Length and diameter of the inorganic fibers are not subject per se toany particular restrictions. Preference is given to using inorganicfibers whose maximum diameter is in the range from 10 nm to 5 mm.

The internal structure of the inorganic fibers can be chosen freely;thus, the fillers can be compact in the sense that they have no internalvoids, but they can also have internal voids. In one variant, theinternal voids of the fibers have maximum diameters in the range from 10to 1000 nm.

In an embodiment, the composite materials of the invention comprisesubstances which improve the fire retardant properties. This can beachieved on the one hand in that the compounds (ii) already have per sea positive influence on the flame retardant properties of the compositematerials, or on the other hand by integrating further substances intothe composite materials, which can particularly advantageously be doneduring the course of the phase inversion polymerization. An example ofsuch suitable flame retardant additives is the flame retardant VP 5453/4from Cognis.

In an embodiment, one or more additives selected from the groupconsisting of flame retardant additives, hydrophobicizing agents andbiocides are integrated into the composite materials.

The composite materials of the invention have a low thermal conductivitycombined with a high mechanical strength. This makes the materialsparticularly attractive for use as structural, mechanically load-bearingthermal insulation materials.

The Epoxy Resins (E)

The epoxide compounds (E) are polyepoxides having an average of at leasttwo terminal or lateral epoxide groups per molecule. These epoxidecompounds can be either saturated or unsaturated and also aliphatic,cycloaliphatic, aromatic or heterocyclic and can also have hydroxylgroups. They can also comprise substituents which do not cause anyinterfering secondary reactions under the mixing and reactionconditions, for example alkyl or aryl substituents, ether groups and thelike.

These epoxide compounds are preferably polyglycidyl ethers based onpolyhydric, preferably dihydric alcohols, phenols, hydrogenationproducts of these phenols and/or of novolacs (reaction products ofmonohydric or polyhydric phenols with aldehydes, in particularformaldehyde, in the presence of acid catalysts).

The epoxide equivalent weights of these epoxide compounds are preferablyin the range from 85 to 3200, in particular from 170 to 830. The epoxideequivalent weight of a substance is the amount of the substance (ingram) which comprises 1 mol of oxirane rings.

As polyhydric phenols, preference is given to the following compounds:resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A),isomer mixtures of dihydroxydiphenylmethane (bisphenol F),tetrabromobisphenol A, 4,4′-dihydroxy-diphenylcyclohexane,4,4′-dihydroxy-3,3-dimethyldiphenylpropane, 4,4′-dihydroxybiphenyl,4,4′-dihydroxybenzophenol, 1,1-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)isobutane, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, etc., and alsothe chlorination and bromination products of the abovementionedcompounds; bisphenol A is very particularly preferred.

The polyglycidyl ethers of polyhydric alcohols are also suitable ascompounds (E). Examples of such polyhydric alcohols are ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,polyoxypropylene glycols (n=1−20), 1,3-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerol,isosorbide and 2,2-bis(4-hydroxycyclohexyl)propane.

It is also possible to use polyglycidyl ethers of polycarboxylic acidsas compounds (F); these are obtained by reacting epichlorohydrin orsimilar epoxy compounds with an aliphatic, cycloaliphatic or aromaticpolycarboxylic acid such as oxalic acid, succinic acid, adipic acid,glutaric acid, phthalic acid, terephthalic acid, hexahydrophthalic acid,2,6-naphthalenedicarboxylic acid and dimerized linolenic acid. Examplesare diglycidyl adipate, diglycidyl phthalate and diglycidylhexahydrophthalate.

It is also possible to use mixtures of a plurality of epoxide compounds(E).

In the production of nanoporous polymer foams in which, as indicatedabove, the hardeners (H) according to the invention are reacted inaqueous medium with epoxide compounds (E) in a phase inversionpolymerization (PIP), additional additives and/or processing aids knownfor this purpose to a person skilled in the art can optionally be used.Examples are pigments, cement, gravel, deaerators, antifoams,dispersants, antisedimentation agents, accelerators, free amines,leveling additives, conductivity improvers.

The Epoxy Resin Hardeners (H)

For the purposes of the present invention, amphiphilic epoxy resinhardeners (H) are epoxy resin hardeners which have hydrophilic andhydrophobic structural elements.

Preference is given to using amphiphilic epoxy resin hardeners which areself-emulsifying in water at 25° C. and are also able to emulsify epoxyresins (E) in water at 25° C.

Preference is given to using hardeners (H) which can be obtained byreacting a mixture comprising

-   -   (A) at least one epoxidized polyalkylene oxide selected from the        group consisting of epoxidized polyethylene oxides, epoxidized        polypropylene oxides and polyethylene-propylene oxides,    -   (B) at least one epoxidized aromatic hydroxyl compound selected        from the group consisting of bisphenol A epoxides and bisphenol        F epoxides and    -   (C) at least one aromatic hydroxyl compound selected from the        group consisting of bisphenol A and bisphenol F        to form an intermediate and subsequently reacting this        intermediate with a polyamine (P).

In an embodiment, exclusively the components (A), (B) and (C) arereacted to form the intermediate and the latter is reacted further witha polyamine (P).

In a further embodiment, the intermediate which is subsequently reactedwith the polyamines (P) to form the hardener is prepared using thecompounds (D) in addition to the compounds (A), (B) and (C). Thecompounds (D) are compounds selected from the group consisting oftriglycidyl ethers of triols and diglycidyl ethers of diols. Examples ofsuitable diols and triols on which the compounds (D) can be based are:ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol,1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, neopentylglycol, 1,2,6-hexanetriol, glycerol and trimethylolpropane.

The Compounds (A)

For the purposes of the invention, epoxidized polyethylene oxides arecompounds which can be obtained by converting the two terminal OH groupsof polyethylene oxide into oxirane groups, for example by reaction withepichlorohydrin. The polyethylene oxide used can have an averagemolecular weight in the range from 80 to 3000; it can be prepared bystarting the polymerization of ethylene oxide on an alkylenediol havingfrom 2 to 18 carbon atoms in the manner known to those skilled in theart.

For the purposes of the invention, epoxidized polypropylene oxides arecompounds which can be obtained by converting the two terminal OH groupsof polypropylene oxide into oxirane groups, for example by reaction withepichlorohydrin. The polypropylene oxide used can have an averagemolecular weight in the range from 110 to 3000; it can be prepared bystarting the polymerization of the propylene oxide on an alkylenediolhaving from 2 to 18 carbon atoms in the manner known to those skilled inthe art.

For the purposes of the invention, polyethylene-propylene oxides arecompounds which can be obtained by converting the two terminal OH groupsof polyethylene-propylene oxide into oxirane groups, for example byreaction with epichlorohydrin. The polyethylene-propylene oxide used canhave an average molecular weight in the range from 80 to 3000. For thepurposes of the present invention, the term polyethylene-propylene oxiderefers to compounds which can be obtained by copolymerization ofethylene oxide and propylene oxide, with the polymerization of the tworeactants being able to be carried out simultaneously or blockwise andthe polymerization of the propylene oxide and/or ethylene oxide beingstarted on an alkylenediol having from 2 to 18 carbon atoms in themanner known to those skilled in the art.

The compounds (A) can be used individually or in admixture with oneanother.

The Compounds (B)

For the purposes of the invention, bisphenol A epoxides are, as isgenerally customary, compounds which can be obtained by reactingbisphenol A with epichlorohydrin and/or polymerizing this by furtherreaction with bisphenol A. These compounds are therefore also known asbisphenol A diglycidyl ethers or generally as epoxy resins. Commercialproducts are Epikote 828, 1001, 1002, 1003, 1004, etc., from Shell.

The molecular weights of the bisphenol A epoxides used are preferably inthe range from 380 to 3000.

For the purposes of the invention, bisphenol F epoxides are, as isgenerally customary, compounds which can be obtained by reactingbisphenol F with epichlorohydrin and/or polymerizing this by furtherreaction with bisphenol F. These compounds are therefore also known asbisphenol F diglycidyl ethers or generally as bisphenol F epoxy resins.

The molecular weights of the bisphenol F epoxides used are preferably inthe range from 350 to 3000.

The compounds (B) can be used individually or in admixture with oneanother.

The Compounds (C)

Bisphenol A is adequately known to those skilled in the art and isrepresented by the following formula:

Bisphenol F is likewise adequately known to those skilled in the art.

The compounds (C) can be used individually or in admixture with oneanother.

The Compounds (P)

Polyamines (P) used for the purposes of the present invention areprimary and/or secondary amines having at least two nitrogen atoms andat least two active amino hydrogen atoms per molecule. It is possible touse aliphatic, aromatic, aliphatic-aromatic, cycloaliphatic andheterocyclic diamines and polyamines. Examples of suitable polyamines(P) are:

polyethylenamines (ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, etc.),1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine,1,5-pentanediamine, 1,3-pentanediamine, 1,6-hexanediamine,3,3,5-trimethyl-1,6-hexanediamine, 3,5,5-trimethyl-1,6-hexanediamine,2-methyl-1,5-pentanediamine, bis(3-aminopropyl)amine,N,N′-bis(3-aminopropyl)-1,2-ethanediamine,N-(3-aminopropyI)-1,2-ethanediamine, 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, aminoethylpiperazines,poly(alkylene oxide)diamines and triamines, (e.g. Jeffamine D-230,Jeffamine D-400,Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-403,Jeffamine EDR-148, Jeffamine EDR-192, Jeffamine C-346, Jeffamine ED-600,Jeffamine ED-900, Jeffamine ED-2001), meta-xylylenediamine,phenylenediamine, 4,4′-diaminodiphenylmethane, toluenediamine,isophoronediamine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane,4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane,1,3-bis(amino-methyl)cyclohexane, the mixture ofpoly(cyclohexylaromatic) amines linked via a methylene bridge (alsoknown as MBPCAA) and polyaminoamides. Polyethyleneamines, in particulardiethylenetriamine, are particularly preferred.

The compounds (P) can be used individually or in admixture with oneanother.

Preparation of the Intermediate

In an embodiment, the intermediate is prepared using the compounds (A)and (B) in a molar ratio of from 0.1:1 to 5:1.

In an embodiment, the intermediate is prepared using a molar ratio ofthe sum of the compounds (A) and (B) (these compounds each comprise twooxirane groups per molecule) to compound C (this compound comprises twoOH groups per molecule) in the range from 1.1:1 to 10:1. In other words,the ratio of equivalents of oxirane rings in the sum of the compounds(A) and (B) to reactive hydrogen atoms of the compound (C) is set to avalue in the range from 1.1:1 to 10:1.

In a further embodiment, namely in cases where at least one compound (D)is also used during the course of the preparation of the hardener, amolar ratio of the sum of the compounds (A), (B) and (D) (thesecompounds each comprise two oxirane groups per molecule) to compound C(this compound comprises two OH groups per molecule) in the range from1.1:1.0 to 10.0:1.0 is set during the preparation of the intermediate.In other words, the ratio of equivalents of oxirane rings in the sum ofthe compounds (A), (B) and (D) to reactive hydrogen atoms of thecompound (C) is set to a value in the range from 1.1:1.0 to 10.0:1.0.

In the interests of clarity, we offer the following explanation: Aperson skilled in the art will be familiar with the expression “ratio ofequivalents”. The fundamental concept underlying the term equivalent isthat the reactive groups on a substance participating in a reactionwhich participate in the desired reaction are considered. The reportingof a ratio of equivalents expresses the numerical ratio of the totalityof the reactive groups of the compounds (x) and (y) used. Here, it hasto be noted that for the present purposes a reactive group is thesmallest possible group capable of reacting; the term reactive group isthus not equivalent to the term functional group. In the case of H-acidcompounds, this means, for example, that although OH groups or NH groupsare such reactive groups, NH₂ groups in which two reactive H atoms arelocated on the same nitrogen atom are not. Here, the two hydrogen atomswithin the functional group NH₂ are regarded as reactive group, so thatthe functional group NH₂ has two reactive groups, namely the hydrogenatoms.

In an embodiment, the preparation of the intermediate is carried out inthe presence of a catalyst, in particular triphenylphosphine orethyltriphenylphosphonium iodide. Here, the amount of the catalyst isfrom about 0.01 to 1.0% by weight, based on the total amount of thecompounds (A), (B) and (C).

The epoxide number (%EpO) of the intermediate is preferably below 10%EpO, in particular below <5% EpO. The definition of the epoxide numberand the details regarding the analytical determination can be found inthe examples section of the present patent application.

Preparation of the Hardener (H)

As indicated above, the hardener is prepared by reacting theintermediate with a polyamine (P).

In an embodiment, the intermediate and the polyamine (P) are used insuch amounts that the ratio of equivalents of the reactive H atoms onthe amino nitrogen atoms of (P) to the oxirane groups in theintermediate is in the range from 4:1 to 100:1.

The reaction of the intermediate with the polyamine is preferablycarried out with an excess of the polyamine being initially charged, sothat it is ensured that essentially 1 molecule of the polyamine,preferably diethylenetriamine, reacts in each case with one of theepoxide groups of the intermediate compound. Excess amine can bedistilled off in order to keep the content of free amine as low aspossible.

The Phase Inversion Polymerization (PIP)

For the purposes of the present invention, a phase inversionpolymerization (PIP) is as follows: An aqueous emulsion of the epoxyresin (E) in water is firstly produced, with the amphiphilic epoxy resinhardener (H) functioning as emulsifier. This system, hereinafter alsoreferred to as reaction system, is initially an oil-in-water emulsion(O/W emulsion). The oil component of this O/W emulsion is of course theepoxy resin. During the subsequent reaction of resin and hardener(curing in the sense of a polyaddition), a phase inversion occurs, i.e.the reaction system changes from an emulsion of the O/W type to one ofthe W/O type in which water is enclosed as disperse phase by the curingpolymer. This is due to the fact that the original emulsifier propertiesof the hardener change during the course of curing since the hardenerbecomes increasingly hydrophobic due to the polyaddition.

After complete curing, a porous polymer matrix which comprises the waterphase in the cavities of the organic matrix is present. The water phasecan, if desired, be removed by drying, forming air-filled cavities. Anecessary condition for this is that a phase inversion polymerizationhas taken place and that no water can escape from the reaction system.This can be realized industrially in various ways.

Firstly, the reaction system can be introduced into a closed mold. It isalso possible to introduce the reaction system into an open system andthen, for example, ensure that (a) there is sufficient atmospherichumidity present at the interface to the gas phase (usually surroundingair) to prevent drying of or loss of water from the upper layer of thereaction system or that (b) the interface to the gas phase is covered,for example by a polymer film.

While the above-described variants for carrying out the PIP areloss-free embodiments, there is a further variant for carrying out thePIP in which although the reaction system is introduced into an opensystem, no particular precautions are taken to prevent loss of waterfrom the interface to the gas phase. In this case, a dense,chemicals-resistant structure (which can be referred to as clearvarnish) is formed at this interface by loss of water and forms a waterbarrier for the part of the reaction system located underneath, so thatthe PIP can take place unhindered in this. After complete curing of thereaction system, the dense, chemicals-resistant layer (which isgenerally from 0.1 to 0.3 mm thick) can then be removed by mechanicalmeans.

It can be seen visually that the cured systems are nanoporous structuresfrom the fact that the materials obtained are not clear but white.

In a preferred embodiment, the PIP is carried out using the epoxy resin(E) and the hardener (H) in a ratio of equivalents of from 2:1 to 1:2.Here, ratios of equivalents of (E) to (H) of 1:1 are particularlypreferred.

The PIP is characterized by an initial phase in which an O/W emulsion ispresent and a curing phase whose commencement is indicated by theformation of the W/O emulsion. The PIP can be carried out at anatmospheric humidity of from 0 to 100%. The water content of the PIPreaction system can be varied in the range from 95 to 20% by weight(based on the total reaction system).

If desired, thickeners can also be added to the reaction system.

Curing of the reaction system can be carried out in a wide temperaturerange, preferably from 1° C. to 99° C. and in particular from 5° C. to60° C.

As indicated above, in one embodiment, the composite material of theinvention comprises the components (i) and (ii) in such a way that thecomponent (ii) is embedded in a matrix of the component (i), withpreference being given to introducing the component (ii) during thecourse of the production of the component (i) by phase inversionpolymerization. This means that the component (ii), i.e. fibers and/orfillers, is added to the PIP reaction system aimed at producing thecomponent (i). Examples of suitable substances for the component (ii)are, in particular:

-   -   as fillers: mineral materials such as cellular, closed-cell or        open-cell, mineral structures (e.g. mineral foams such as        mineral foam boards from Sto) or Ytong bricks in comminuted        foam, vermiculite and other clay minerals, or other porous rocks        and also expanded glass granules (Perlite), inorganic fillers        such as carbon nanotubes from Bayer, Sipermate from Degussa,        silicic acids, silica, zeolites;    -   as fibers: glass fibers but also natural fibers such as        sepiolite and wollastonite.

EXAMPLES Abbreviations

In the following:

-   -   EEW=epoxide equivalent weight (as described above)    -   MW=average molecular weight    -   RPM=revolutions per minute    -   %=percent by weight, unless explicitly indicated otherwise

Raw Materials Used

Epoxy resin (E): Chem Res E20 (Cognis GmbH)Hardener (H): the following hardener H1 was prepared:

Hardener H1

44 g of poly(propylene glycol) diglycidyl ether (EEW: 326 and MW: 652)were mixed at 20 degrees celsius with 46.2 g of bisphenol A diglycidylether (Chemres E20 from Cognis EEW: 194), 14.0 g of bisphenol A and 0.1g of triphenylphosphine. The mixture obtained in this way was heated to160° C. and stirred at this temperature for about 3.5 hours until theepoxide number was 3.95%. It was subsequently cooled to 60° C. and 121.4g of diethylenetriamine were added at this temperature. After theexothermic reaction had abated, the reaction mixture was again heated at160° C. for 2 hours. The excess of diethylenetriamine was distilled offunder reduced pressure (to a temperature at the bottom of 200° C. andpressures of less than 10 mbar) until no more free amine distilled over.The mixture was subsequently cooled to 90° C. and admixed with 89.5 g ofwater while stirring well.

This gave 205.6 g of a clear amber-colored liquid having a viscosity(neat, Brookfield, 10 rpm, 40° C.) of 2140 mPas, a solids content of 60%and an amine number of 134.

Use Example

Epoxy resin (E) and hardener (H) were placed in a stirred beaker(diameter 95 mm, height 120 mm) and preemulsified by means of aPendraulik stirrer model LM34 at setting 1 (about 465revolutions/minute). The amount of (E) and (H) used are shown intable 1. A homogeneous white coloration indicated appropriatehomogenization. Water (the respective amount of water is shown intable 1) was subsequently added in portions. The stirrer speed was setso that there was just no formation of a clot. After homogenizing for 5minutes, the filler was carefully stirred into the prepared emulsionusing a spatula. The total time from preemulsification to processing wasabout 7 minutes. The experiment was carried out using a ratio ofequivalents of epoxy resin to hardener of 1:1.

Details of example 1 may be found in table 1.

Provision of Specimens

The plate for the thermal conductivity measurement was produced in aTeflon mold coated with the mold release agent Loxiol G40 (from Cognis).The casting composition was covered until removed from the mold, but notclosed so as to be airtight. The test specimen was removed from the moldafter 48 hours, and drying required about 48 hours at 55° C.

Thermal Conductivity Measurement

The thermal conductivity was measured in accordance with ISO 8301; thiscorresponds to the heat flow measurement method. The plate dimensionswere 150 mm×150 mm, and the layer thickness varied from 20 mm to 25 mm.A measuring apparatus model HFM 436/3/1E from NETZSCH was used for themeasurement, and the contact pressure was 65N. The measurementtemperature chosen was 10° C. with a temperature difference of 20 K.This is a standard measurement for thermal insulation materials. Thesample was stored at room temperature for at least 72 hours before themeasurement; special storage under standard conditions did not takeplace.

TABLE 1 Examples: Example 1 Hardener H1 [g] 125 Chem Res E20 [g] 113.1Mineral foam, comminuted 89.4 Water, d.i. + 1% of Bentone EW [g] 1015.9Binder content [%} 15.0 Curing temperature 55° C. Density [g/cm³] 0.17Thermal conductivity [W/m * K] 0.039 Notes: (1) The line “bindercontent” serves merely for information. The binder here is simply thereaction product of hardener H1 and epoxy resin (Chem Res E20). Thebinder content is accordingly the percentage of the binder defined inthis way in the total system. The calculation of the binder content forexample 1 may be demonstrated by way of example: Since the reaction ofepoxy resin with amine hardener (hardener H1) proceeds as a polyadditionwithout elimination of parts of molecules, the proportions by mass ofresin and hardener are to be added up in order to obtain the amount ofthe resulting binder: The epoxy resin Chemres E 20 used is to be takeninto account on a 100% basis (113.1). Since the hardener H1 used has asolids content of 60%, only 0.6 × 125.0 g = 75.0 g of this has to betaken into account. This gives the amount of binder in the system as75.0 g + 113.1 g = 188.1 g. The total system additionally comprises1015.9 g of water, and accordingly comprises a total amount of 125 g +113.1 g + 1015.9 g = 1254 g. The proportion of binder in the totalsystem is thus as follows: % of binder = 188.1 × 100/1254 = 15.00%. (2)d.i. means “deionized”

1. A composite material comprising (i) a nanoporous polymer foamobtained by reacting one or more epoxy resins with one or moreamphiphilic epoxy resin hardeners in water in a phase inversionpolymerization, and (ii) one or more inorganic fillers and/or inorganicfibers, with the proviso that hollow glass beads are excluded asfillers.
 2. The composite material according to claim 1, wherein the oneor more amphiphilic epoxy resin hardeners are obtained by reacting amixture comprising: (A) at least one epoxidized polyalkylene oxideselected from the group consisting of epoxidized polyethylene oxides,epoxidized polypropylene oxides and polyethylene-propylene oxides, (B)at least one epoxidized aromatic hydroxyl compound selected from thegroup consisting of bisphenol A epoxides and bisphenol F epoxides and(C) at least one aromatic hydroxyl compound selected from the groupconsisting of bisphenol A and bisphenol F to form an intermediate andsubsequently reacting this intermediate with a polyamine (P).
 3. Thecomposite material according to claim 2, wherein the polyamine (P)comprises diethylenetriamine.
 4. The composite material according toclaim 2, wherein the at least one epoxidized polyalkylene oxidecomprises an epoxidized polypropylene oxide.
 5. The composite materialaccording to claim 2, wherein the at least one epoxidized aromatichydroxyl compound comprises a bisphenol A expoxide.
 6. The compositematerial according to claim 2, wherein the at least one aromatichydroxyl compound comprises bisphenol A.
 7. The composite materialaccording to claim 1, wherein the composite material comprises component(ii) in an amount in the range from 2 to 90% by volume, based on thetotal volume of the composite material.
 8. The composite materialaccording to claim 2, wherein component (ii) has heat-insulatingproperties.
 9. The composite material according to claim 2, wherein oneor more additives selected from the group consisting of flame retardantadditives, hydrophobicizing agents, and biocides are integrated into thecomposite material.
 10. A method of thermally insulating in transportmeans or in industrial and plant construction, the method comprisingobtaining the composite material according to claim 1; and providing thecomposite material as a thermal insulation material in transport meansor in industrial and plant construction.
 11. The composite material ofclaim 1, wherein the nanoporous polymer foam has a thermal conductivityof 0.09 W/m*K or less and a maximum compressive stress of 1.0 MPa orabove.
 12. The method of claim 10 having a thermal conductivity of 0.09W/m*K or less and a maximum compressive stress of 1.0 MPa or above.